Title of Invention

PROCESS FOR PRODUCTION OF (METH) ACRYLIC ACID

Abstract The invention is for a process for producing (meth)acrylic acid comprising a first step of producing (meth)acrolein as a main product from at least one reaction material selected from the group consisting of propylene, isobutylene, t-butyl alcohol and methyl-t-butyl ether, and a second step of producing (meth)acrylic acid from the (meth)acrolein, wherein yield of (meth)acrylic acid in the product of the first step is 20 mole % or higher, wherein a Mo—Bi—Nb—Te based composite metal oxide is used as a catalyst of the first step and the composite metal oxide is represented by the following Formula 1: [Formula 1] MoaBibNbcTedFe1CogKjOk Wherein Mo represents molybdenum, Bi represents bismuth, Nb represents niobium, Te represents tellurium, Fe represents iron, Co represents cobalt, K represents potassium, and O represents oxygen; each of a, b, c, d, f, g, j and k represents the atomic ratio of each element; wherein when a=12, b is 0.01-20, c is 0.001-20, d is 0.001-20, f is 1.2, g is 4.5 or 5, j is 0.05, and k is a number defined by the oxidation state of each of the above elements.
Full Text

Technical Field
5 The present invention relates to a Mo-Bi-Nb-Te
based composite metal oxide, and a process for producing
(meth) acrylic acid from propylene or the like by using
the Mo-Bi-Nb-Te based composite metal oxide as a
catalyst. Also, the present invention relates to a
10 process for producing (meth)acrylic acid comprising a
first step of producing (meth)acrolein as a main product
from propylene or the like, and a second step of
producing (meth)acrylic acid from the (meth)acrolein,
wherein the yield of (meth)acrylic acid in the product
15 of the first step is 20 mole% or higher.
Background Art
A process for producing an unsaturated fatty acid
from an olefin by way of an unsaturated aldehyde is a
20 typical process of catalytic vapor phase oxidation. To
perform partial oxidation of olefins, composite oxides
containing molybdenum and bismuth, molybdenum and
vanadium, or mixtures thereof are used as catalysts.
Particular examples of such catalytic vapor phase
25 oxidation include a process of producing (meth)acrylic
acid by the oxidation of propylene or isobutylene by way
of (meth)acrolein, a process of producing phthalic
anhydride by the oxidation of naphthalene or
orthoxylene, and a process of producing maleic anhydride
30 by the partial oxidation of benzene, butylene or
butadiene.
Generally, (meth)acrylic acid, a final product, is
produced from at least one reaction material selected
from the group consisting of propylene, propane,
35 isobutylene, t-butyl alcohol or methyl-t-butyl ether

(referred to as ^propylene or the like' , hereinafter) by
a two-step process of vapor phase catalytic partial
oxidation. More particularly, in the first step,
propylene or the like is oxidized by oxygen, inert gas
for dilution, water steam and a certain amount of a
catalyst, so as to produce (meth) acrolein as a main
product. Then, in the second step, the (meth)acrolein is
oxidized by oxygen, inert gas for dilution, water steam
and a certain amount of a catalyst, so as to produce
(meth)acrylic acid. The catalyst used in the first step
is a Mo-Bi-based multinary metal oxide, which oxidizes
propylene or the like to produce (meth)acrolein as a
main product. Also, some acrolein is continuously
oxidized on the same catalyst to partially produce
(meth)acrylic acid. The catalyst used in the second step
is a Mo-V-based multinary metal oxide, which mainly
oxidizes (meth)acrolein in the mixed gas containing the
(meth)acrolein produced from the first step to produce
(meth)acrylic acid as a main product.
A reactor for performing the aforementioned
process is provided either in such a manner that both
the two-steps can be performed in one system, or in such
a manner that the two steps can be performed in
different systems.
As mentioned hereinbefore, the first-step catalyst
involved in vapor phase partial oxidation using
propylene or the like as a starting material is a
multinary metal oxide, with which (meth)acrolein is
produced as a main product and at most 10% of
(meth)acrylic acid is produced.
As disclosed in Japanese Laid-Open Patent No.
Hei8-3093, a conventional first-step catalyst is a
composite oxide represented by the formula of Moa-Bib-
Fec-Ad-Be-Cf-Dg-Ox, wherein Mo, Bi and Fe represent
molybdenum, bismuth and iron, respectively; A is nickel

and/or cobalt; B is at least one element selected from
the group consisting of manganese, zinc, calcium,
magnesium, tin and lead; C is at least one element
selected from the group consisting of phosphorus, boron,
arsenic, Group 6B elements in the Periodic Table,
tungsten, antimony and silicon; D is at least one
element selected from the group consisting of potassium,
rubidium, cesium and thallium; each of a, b, c, e, f and
g is a number satisfying the conditions of 0 0 and x is a value defined by the oxidation state of each
element. When vapor phase catalytic oxidation of
propylene is performed with molecular oxygen by using
the above first-step catalyst and by operating the
first-step catalyst layer at a temperature of 325°C,
acrolein is produced with a yield of 81.3% and acrylic
acid is produced with a yield of 11%. In other words,
acrylic acid content is low in the reaction product
obtained by using the first-step catalyst.
Meanwhile, Japanese Laid-Open Patent No. Hei5-
293389 discloses a catalyst represented by the formula
of MOaBibFecAdXeYfZgSih0i, wherein Mo, Bi, Fe, Si and 0
represent molybdenum, bismuth, iron, silicon and oxygen,
respectively; A is at least one element selected from
the group consisting of cobalt and nickel; X is at least
one element selected from the group consisting of
magnesium, zinc, manganese, calcium, chrome, niobium,
silver, barium, tin, tantalum and lead; Y is at least
one element selected from the group consisting of
phosphorus, boron, sulfur, selenium, Group 6B elements
in the Periodic Table, cerium,' tungsten, antimony and
titanium; Z is at least one element selected from the
group consisting of lithium, sodium, potassium,
rubidium, cesium and thallium; and each of a, b, c, d,

e, f, g, h and i represents the atomic ratio of each
element, with the proviso that when a=12, b= 0.01 — 3,
c=0.01~5, d=l~12, e=0~6, f=0~5, g=0.001-1,
h=0~20, and i is the oxygen atom number needed to
satisfy the atomic valence of each element. When vapor
phase catalytic oxidation of propylene is performed by
using the above first-step catalyst to produce acrolein
and acrylic acid, acrylic acid is produced with a yield
of 6.2 mole% under a propylene conversion ratio of 99.1
mole% and an acrolein selectivity of 89.6 mole%. In
other words, acrylic acid content is still low in the
reaction product obtained by using the first-step
catalyst.
In a process for producing (meth)acrylic acid, the
temperature of the second-step catalyst layer varies
depending on the selectivity of (meth) acrolein and
(meth)acrylic acid (i.e. the first-step catalytic
reaction product) and the amount of (meth)acrolein
unreacted in' the second-step catalytic reaction. The
second-step catalyst layer is operated in such a manner
that unreacted (meth)acrolein can be minimized. When
(meth)acrolein selectivity is high in the first-step
catalytic reaction product, the second-step catalyst
layer is subjected to an increased load and
concentration, resulting in an increase in reaction
temperature and degradation of the lifetime of the
catalyst. Additionally, when a concentration of
unreacted (meth)acrolein is increased due . to the
degradation in catalytic activity, a waste gas
incineration system (WGIS) may be overloaded, resulting
in degradation of the lifetime of a waste gas treating
catalyst.
Disclosure of the Invention
Therefore, the present invention has been made in

view of the above-mentioned problems. The inventors of
the present invention have found that when a Mo-Bi-Nb-Te
based composite metal oxide is used as the first-step
catalyst in the production of (meth)acrylic acid from
propylene or the like, yield and/or selectivity of
(meth)acrylic acid increases in the first-step reaction
product, and thus (meth)acrolein load and concentration
decrease in the second-step to such a degree that
(meth)acrolein conversion ratio can reach 100%. The
present invention is based on this finding.
According to an aspect of the present invention,
there is provided a Mo-Bi-Nb-Te based composite metal
oxide.
According to another aspect of the present
invention, there is provided a process for producing
(meth)acrylic acid from at least one reaction material
selected from the group consisting of propylene,
propane, isobutylene, t-butyl alcohol and methyl-t-butyl
ether by using a Mo-Bi-Nb-Te based composite metal oxide
as a catalyst.
According to still another aspect of the present
invention, there is provided a process for producing
(meth)acrylic acid comprising a first step of producing
(meth) acrolein as a main product from at least one
reaction material selected from the group consisting of
propylene, propane, isobutylene, t-butyl alcohol and
methyl-t-butyl ether, and a second step of producing
(meth)acrylic acid from the (meth)acrolein, wherein
yield of (meth) acrylic acid in the product of the first
step is 20 mole% or higher.
Hereinafter, the present invention will. be
explained in more detail.
Mo-Bi-based first-step metal oxide catalysts for
producing (meth)acrolein from propylene or the like,
which have been disclosed to date, generally provide a

conversion ratio (selectivity) from propylene or the
like to (meth) acrolein and (meth) acrylic acid of about
90% or more, wherein the molar ratio of (meth)acrolein
to (meth)acrylic acid in the first-step reaction product
is about 9:1. Additionally, when the first-step reaction
product is subjected to the second-step reaction, it is
possible to obtain a (meth)acrolein conversion ratio of
about 98%.
The inventors of the present invention have found
that when a Mo-Bi-based composite oxide also containing
both Nb and Te, i.e. a Mo-Bi-Nb-Te based composite metal
oxide is prepared and used as the first-step reaction
catalyst, it is possible to obtain a conversion ratio
(selectivity) of (meth)acrolein and (meth)acrylic acid
from propylene or the like of 90% or more, as well as a
molar ratio of (meth)acrolein to (meth)acrylic acid in
the first-step reaction product of approximately
8:2-7:3.
Additionally, the inventors of the present
invention have found that use of a Mo-Bi-Nb-Te based
composite metal oxide as the first-step catalyst
provides a decreased selectivity of (meth)acrolein in
the first-step reaction product and an increased
selectivity of (meth)acrylic acid as mentioned above,
and thus the second-step reaction is subjected to a
decreased load and concentration of (meth)acrolein as a
reactant, so that the second-step reaction can provide a
(meth)acrolein conversion ratio of 100% after the
completion of the reaction.
Further, according to the present invention, since
selectivity of (meth)acrylic acid increases from
(meth)acrolein and (meth)acrylic acid, which are the
main reaction products that have passed through the
first-step catalyst, complete conversion of

(meth)acrolein can be accomplished in the subsequent
second-step catalytic reaction step. Hence, it is
possible to operate the overall process under a high
load and concentration so as to provide a high yield,
and to improve the lifetime of the second-step catalyst.
In brief, the present invention is based on the
fact that a Mo-Bi-Nb-Te based composite metal oxide,
used as the first-step reaction catalyst in a process
for producing (meth)acrylic acid from propylene or the
like, provides a lower (meth)acrolein selectivity and a
higher (meth)acrylic acid selectivity in the first-step
reaction product, when compared to other conventional
Mo-Bi metal oxides currently used as the first-step
catalyst.
(1) Preferably, the Mo-Bi-Nb-Te based composite
metal oxide according to the present invention is a
composite metal oxide represented by the following
Formula 1:
[ Formula 1]
Moa Bib Nbc Ted Ae Bf Cg Dh Ej. Fj 0k
Wherein Mo represents molybdenum, Bi represents
bismuth, Nb represents niobium, and Te represents
tellurium;
A is at least one element selected from the group
consisting of W, Sb, As, P, Sn and Pb;
B is at least one element selected from the group
consisting of Fe, Zn, Cr, Mn, Cu, Ru, Pd, Ag and Ru;
C is at least one element selected from the group
consisting of Co, Cd, Ta, Pt and Ni;
D is at least one element selected from the group
consisting of Si, Al, Zr, V and Ce;
E is at least one element selected from the group
consisting of Se, Ga, Ti, Ge, Rh and Au;
F is at least one element selected from the group
consisting of Na, K, Li, Rb, Cs, Ca, Mg, Sr, Ba and MgO;

each of a, b, c, d, e, f, g, h, i, j and k
represents the atomic ratio of each element;
wherein when a=12, b is 0.01-20, c is 0.001-20, d
is 0.001-20, e is 0-15, f is 0-20, g is 0-20, h is 0-10,
i is 0-10, j is 0-10, and k is a number defined by the
oxidation state of each of the above elements.
When used as a catalyst, the Mo-Bi-Nb-Te based
composite metal oxide according to the present invention
may be used alone or may be supported on an inert
carrier. Particular examples of the carrier that may be
used in the present invention include porous or non-
porous alumina, silica-alumina, silicon carbide, '
titanium dioxide, magnesium oxide, aluminum sponge, or
the like. Additionally, the carrier may take a
cylindrical shape, a hollow cylindrical shape or a
spherical shape, but is not limited thereto. For
example, a catalyst having a cylindrical shape
preferably has a ratio of length to diameter (outer
diameter) (L/D ratio) of 1~ 1.3, and more -preferably has
a L/D ratio of 1. A catalyst having a cylindrical or
spherical shape preferably has an outer diameter of
3~ 10mm, more preferably of 5~ 8mm.
The Mo-Bi-Nb-Te based composite metal oxide
according to the present invention may be prepared by a
conventional method for producing a composite metal
oxide, except that a different composition of elements
is used. '
There is no particular limitation in the shape of
a metal precursor forming the Mo-Bi-Nb-Te based
composite metal oxide. For example, a compound that is
provided originally in the form of an oxide or can be
converted into an oxide by heating (i.e. calcination) at
least in the presence of oxygen, for example,
halogenide, nitride, formate, oxalate, citrate, acetate,

carbonate, amine complex, ammonium salt and/or hydroxide
may be used as a starting material.
According to an embodiment of the present
invention, the method for preparing the composite metal
oxide comprises the steps of: dissolving or dispersing a
predetermined amount (stoichiometric amount) of each
starting material containing each element forming the
composite metal oxide into an aqueous medium; heating
the resultant solution or dispersion while stirring it;
allowing the system to evaporate to obtain a dry solid
and drying and pulverizing the solid; and molding the
powder into a desired shape via extrusion molding to
obtain tablets or granules. In this case, glass fibers
and inorganic fibers including various kinds of
whiskers, which are known to improve the strength and
frictional resistance, may be further added.
Additionally, in order to control the properties of the
catalyst and to obtain excellent reproducibility, other
additives known as powder binders, such as ammonium
nitrate, cellulose, starch, polyvinyl alcohol, stearic
acid, or the like, may be used.
The composite metal oxide catalyst according to
the present invention may be obtained by calcining the
molded product obtained as described above or the same
product supported on a carrier under a flow of 0.2~ 2m/s
at 300~ 600°C for about i~ 10 hours. The calcination step
may be performed under an inert gas atmosphere, an
oxidative atmosphere, for example, air (a mixture of
inert gas and oxygen), or a reductive atmosphere (e.g.,
a mixture of inert gas, oxygen and NH3, CO and/or H2) .
The calcination step may be performed for a period of
several minutes to several hours, and the calcination
period generally decreases as the temperature increases.
(2) The Mo-Bi-Nb-Te based composite metal oxide

according to the present invention may be used as a
catalyst to produce (meth)acrylic acid from at least one
reactant selected from the group consisting of
propylene, propane, isobutylene, t-butyl alcohol, and
metyl-t-butyl ether. In this case, conversion
(selectivity) from propylene or the like into
(meth)acrolein and (meth)acrylic acid may be
accomplished at a ratio of 90% or more, and the molar
ratio of (meth)acrolein:(meth)acrylic acid in the
reaction product is approximately 8:2~ 7:3.
Particularly, the Mo-Bi-Nb-Te based composite
metal oxide according to the present invention may be
used as a catalyst for the first-step partial oxidation
in a process for producing (meth)acrylic acid from a
reaction material such as propylene or the like, the
process comprising a first step for producing
(meth)acrolein as a main product from the reactants such
as propylene or the like and a second step for producing
(meth)acrylic acid from the (meth)acrolein.
When vapor phase catalytic oxidation is carried
out by using the Mo-Bi-Nb-Te based composite metal oxide
according to the present invention as a catalyst, there
is no particular limitation in systems and operation
conditions thereof used in the process. Reactors that
may be used in the present invention include
conventional fixed-bed, fluidized-bed and moving-bed
reactors. For example, the process for producing
(meth)acrylic acid may be performed in a shell-and-tube
reactor and the Mo-Bi-Nb-Te based composite metal oxide
according to the present invention may be packed in a
reaction tube so as to be used as a first-step fixed bed
catalyst. Herein, as a second-step catalyst, Mo-V-based
multinary metal oxide may be used to oxidize
(meth)acrolein-containing mixed product gas generated by

the first-step Mo-Bi-Nb-Te based composite metal oxide
catalyst, thereby producing (meth)acrylic acid.
To perform the reaction, reaction conditions,
which are generally adopted for producing (meth)acrylic
acid and (meth)acrolein from a reaction material such as
propylene or the like via vapor phase catalytic
oxidation, may be used. For example, a gas mixture as a
starting material, which contains 7 vol% or more of
reactants such as propylene or the like, 10- 13 vol% of
molecular oxygen and 60~ 80 vol% of inert gas functioning
as a diluent (e.g. nitrogen, carbon dioxide, steam, or
the like), is caused to be in contact with the catalyst
according to the present invention, at a temperature of
250~ 500°C under a pressure of 0.1- 3 kg/cm2G with a space
velocity of 300- 5000hr_1 (STP) to carry out a desired
reaction.
The second-step catalytic reaction is suitably
carried out at a reaction temperature of 200- 450°C,
preferably of 265- 370CC, under a reaction pressure of
0.1- 10 atm, preferably of 0.5-3 atm. For example, a
feed gas as reactants, which contains 4- 10 vol% of
(meth) acrolein, 10- 13 vol% of oxygen, 5- 60 vol% of
water steam and 20- 80 vol% of inert gas, is introduced
onto the catalyst with a space velocity of 500- 5000hr-1
(STP) to perform oxidation.
(3) Further, the present invention provides a

process for producing (meth)acrylic acid comprising a
first step of producing (meth)acrolein as a main product
from propylene or the like, and a second step of
producing (meth)acrylic acid from the (meth)acrolein,
wherein yield of (meth)acrylic acid in the product of
the first step is 20 mole% or higher.
The yield as high as 20 mol% of (meth)acrylic acid
in the first-step reaction product can be accomplished
by using the Mo-Bi-Nb-Te based composite metal oxide
according to the present invention as the first-step
catalyst.
Meanwhile, when (meth)acrylic acid is produced
with a yield of 20 mole% or higher in the first-step
reaction product, it is possible to obtain a conversion
ratio of (meth)acrolein of 98~ 100%, preferably 100%, in
the second-step reaction. Herein, the (meth)acrolein
conversion ratio as high as 98- 100% also depends on the
content of propylene or the like in the reaction mixture
introduced to the first-step. Preferably, propylene or
the like is contained in the reaction mixture gas
introduced into the first-step reaction in an amount of
7~ 10 vol% in order to accomplish a (meth)acrolein
conversion ratio of 100%.
Mode for Carrying Out the Invention
Reference will now be made in detail to the
preferred embodiments of the present invention. It is to
be understood that the following examples and
comparative examples are illustrative only, and the
scope of the present invention is not limited thereto.

Preparation Example 1: Catalyst 1
First, 2500 ml of distilled water was heated and

stirred at 70°C~ 85°C and lOOOg of ammonium molybdate was
added thereto to form solution (1). Next, 274g of
bismuth nitrate, 228g of ferrous nitrate and 2. 3g of
potassium nitrate were added to 400ml of distilled
water, the materials were mixed thoroughly, 71g of
nitric acid was added thereto, and the materials were
dissolved sufficiently to form solution (2). To 200ml of
distilled water, 686g of cobalt nitrate was dissolved to
form solution (3). After mixing solution (2) with
solution (3), the mixed solution was further mixed with
solution (1) while maintaining the temperature at
40~ 60°C to provide a catalyst suspension.
The catalyst suspension was dried to produce
M012Bi1.2Fe1.2C05Ko.05 and the catalyst was pulverized into a
size of 150fim or less. The resultant catalyst powder was
mixed for 2 hours and formed into a cylindrical shape.
The catalyst was formed to have an outer diameter of
4.0~ 8.0mm, and calcined at 500CC for 5 hours under the
air, and then the catalytic activity was verified.
Preparation Example 2: Catalyst 2
Catalyst 2 was provided in the same manner as
described in Preparation Example 1, except that 63g of
niobium chloride and 150g of tellurium chloride were ■
further added to form solution (1). The catalyst had the
elemental composition", of M012Nbo.5Te1Bi1.2Fe1.2C05Ko.05 except
oxygen.
Preparation Example 3: Catalyst 3
Catalyst 3 was provided in the same manner as
described in Preparation Example 1, except that 127g of
niobium chloride and 150g of tellurium nitrate were
further added to form solution (1). The catalyst had the
elemental composition of Mo12Nb1.0Te1.0Bi1.2Fe1.2Co4.5K0.05

except oxygen.
Preparation Example 4: Catalyst 4
Catalyst 4 was provided in the same manner as
described in Preparation Example 1, except that 63g of
niobium chloride and 75g of tellurium chloride were
further added to form solution (1). The catalyst had the
elemental composition of Mo12Nbo.5Te1Bi1.2Fe1.2Co4.5Ko.05
except oxygen.
Preparation Example 5: Catalyst 5
First, 2000 ml of distilled water was heated and
stirred at 100°C and 246g of ammonium tungstate, lOOOg of
ammonium molybdate and 220g of ammonium vanadate were
dissolved therein to form solution (1). Next, 228g of
copper nitrate and 4 9g of strontium nitrate were added
to 500ml of distilled water, and the materials were
mixed thoroughly to form solution (2) . Solution (1) was
mixed with solution (2) to provide a suspension. The
suspension was treated by using a homogenizer for at
least 30 minutes and was coated on spherical carriers
having an outer diameter of 4.0~ 8.0mm by using a spray
nozzle to an amount of 20- 30 wt% as expressed by the
catalytically active component present in the
suspension. The coated catalyst was dried at 120°C
sufficiently and calcined at 400°C for at least 5 hours
to provide spherical catalyst particles having a final
outer diameter of 5mm(±0.2).
The catalyst had the elemental composition of
Mo12W2.0V4.oCu2.oSr0.5 except oxygen.
Activity Test>

To a 3m stainless steel reactor having an inner
diameter of 1 inch and heated with molten nitrate salt,
alumina silica was packed to a height of 150mm as an
inert material, and any one of Catalysts 1~ 4 was packed
to a height of 2800mm as the first-step catalyst, from
the inlet of the reaction gas toward the outlet.
Then, alumina silica was packed to a height of
150mm as an inert material and Catalyst 5 was packed to
a height of 2900mm as the second-step catalyst.
Propylene was subjected to vapor phase oxidation by
using the reactor to produce acrolein and acrylic acid.
The first-step oxidation was performed by introducing
feed gas containing 7 vol% of propylene, 13 vol% of
molecular oxygen, 8 vol% of water steam and 72 vol% of
inert gas onto the catalyst with a space velocity of
1500 hr-1 (STP), at a reaction temperature of 320°C,
under a reaction pressure of 0.7 atm. The second-step
oxidation was performed at a reaction temperature of
276°C, under a reaction pressure of 0.1~ 3kg/cm2G.
In the following Tables 1 and 2, conversion ratio
of a reaction material, selectivity and yield are
calculated based on the following Mathematical Formulae
1~ 7.
[ Mathematical Formula 1]
first-step propylene conversion ratio(%) = [moles
of reacted propylene/moles of supplied propylene] X 100
[ Mathematical Formula 2]
yield(%) of acrolein in the first step = [moles of
produced acrolein/moles of supplied propylene] X 100
[ Mathematical Formula 3]
yield(%) of acrylic acid in the first step= [moles
of produced acrylic acid/moles of supplied propylene] X

100
[ Mathematical Formula 4]
selectivity(%) of acrolein + acrylic acid in the
first step = [ moles of produced acrolein and acrylic
acid/moles of reacted propylene] X 100
[ Mathematical formula 5]
second-step acrolein conversion ratio(%) = [moles
of reacted acrolein/moles of supplied acrolein] X 100
[ Mathematical Formula 6]
yield(%) of acrylic acid in the second step=
[ moles of produced acrylic acid/moles of supplied
acrolein] X 100
[ Mathematical Formula 7]
selectivity(%) of acrylic acid in the second step
= [ moles of produced acrylic acid/moles of reacted
acarolein] X 100
The experimental results of the Examples according
to the present invention and Comparative Example are
shown in the following Table 1 (first-step oxidation)
and Table 2 (second-step oxidation).



Industrial Applicability
5 As can be seen from the foregoing, when the Mo-Bi-
Nb-Te based composite metal oxide according to the
present invention is used as the first-step catalyst in
the production of (meth)acrylic acid from propylene or
the like, yield and/or selectivity of (meth)acrylic acid
10 Increases in the first-step reaction product, and thus
(meth)acrolein load decreases in the second-step to such
a degree that (meth)acrolein conversion ratio can reach
98- 100%.
While this invention has been described in
15 connection with what is presently considered to be the
most practical and preferred embodiment, it is to be
understood that the invention is not limited to the
disclosed embodiment and the drawings. On the contrary,

it is intended to cover various modifications and
variations within the spirit and scope of the appended
claims.

WE CLAIM:
1. A process for producing (meth) acrylic acid comprising a first step of producing (meth)
acrolein as a main product from at least one reaction material selected from the group consisting of
propylene, isobutylene, t-butyl alcohol and methyl-t-butyl ether, and a second step of producing
(meth) acrylic acid from the (meth) acrolein, wherein yield of (meth)acrylic acid in the product of
the first step is 20 mole % or higher, wherein a Mo-Bi-Nb-Te based composite metal oxide is used
as a catalyst of the first step and the composite metal oxide is represented by the following
Formula 1 :
[Formula 1 ]
MoaBibNbcTedFe1CogKjOk
Wherein Mo represents molybdenum, Bi represents bismuth, Nb represents niobium, Te represents
tellurium, Fe represents iron, Co represents cobalt, K represents potassium, and O represents
oxygen;
each of a, b, c, d, f, g, j and k represents the atomic ratio of each element;
wherein when a= 12, b is 0.01- 20, c is 0.001-20, d is 0.001-20, f is 1.2, g is 4.5 or 5, j is 0.05, and
k is a number defined by the oxidation state of each of the above elements.
2. The process as claimed in claim 1, wherein the first-step reaction product includes (meth)
acrolein and (meth) acrylic acid in a molar ratio ((meth)acrolein : (meth) acrylic acid) of 8:2-7 :3.
3. The process as claimed in claim 1, wherein conversion ratio of (meth) acrolein in the second
step is 98%-100%.
4. The process as claimed in claim 1, wherein the reaction material introduced into the first
step comprises at least one reaction material selected from the group consisting of propylene,
isobutylene, t-butyl alcohol and methyl-t-butyl ether in a concentration of 7-10 vol % .



ABSTRACT


PROCESS FOR PRODUCTION OF (METH)
ACRYLIC ACID
The invention is for a process for producing (meth)acrylic acid comprising a
first step of producing (meth)acrolein as a main product from at least one reaction
material selected from the group consisting of propylene, isobutylene, t-butyl alcohol
and methyl-t-butyl ether, and a second step of producing (meth)acrylic acid from the
(meth)acrolein, wherein yield of (meth)acrylic acid in the product of the first step is 20
mole % or higher, wherein a Mo—Bi—Nb—Te based composite metal oxide is used as
a catalyst of the first step and the composite metal oxide is represented by the following
Formula 1:
[Formula 1]
MoaBibNbcTedFe1CogKjOk
Wherein Mo represents molybdenum, Bi represents bismuth, Nb represents niobium, Te
represents tellurium, Fe represents iron, Co represents cobalt, K represents potassium,
and O represents oxygen;
each of a, b, c, d, f, g, j and k represents the atomic ratio of each element;
wherein when a=12, b is 0.01-20, c is 0.001-20, d is 0.001-20, f is 1.2, g is 4.5 or 5, j is
0.05, and k is a number defined by the oxidation state of each of the above elements.

Documents:

http://ipindiaonline.gov.in/patentsearch/GrantedSearch/viewdoc.aspx?id=92W60vCBwZuJljPDVLkicA==&loc=wDBSZCsAt7zoiVrqcFJsRw==


Patent Number 272128
Indian Patent Application Number 470/KOLNP/2008
PG Journal Number 13/2016
Publication Date 25-Mar-2016
Grant Date 18-Mar-2016
Date of Filing 01-Feb-2008
Name of Patentee LG CHEM, LTD
Applicant Address 20, YOIDO-DONG, YOUNGDUNGPO-GU SEOUL
Inventors:
# Inventor's Name Inventor's Address
1 SHIN HYUN JONG 102-1807, JUNGHEUNG APARTMENT, 331-93 JINWOL-DONG, NAM-GU, GWANGJU 503-841
2 YOO YEON SHICK 504-1202, MUNCHON MAEUL 5-DANJI HANIL APARTMENT, JUYEOP 2-DONG, ILSAN-GU, GOYANG-SI, GYEONGGI-DO 411-747
3 CHOE YOUNG HYUN NA-203, LG CHEMICAL SATAIK, 1, SONGWOL-DONG, NAJU-SI, JEOLLANAM-DO 520-130
4 CHO YOUNG JIN RM 304, DORMITORY OF LG CHEMICALS, 1, SONGWOL-DONG, NAJU-SI, JEOLLANAM-DO 520-130
5 PARK KWANG HO 201-1602, EXPO APARTMENT, JEONMIN-DONG, YUSEONG-GU, DAEJEON 305-761
6 PARK JOO YEON 302-101, SAMIK 3-CHA APARTMENT, JINWOL-DONG, NAM-GU, GWANGJU 503-770
7 KIM DUK KI 207-4, GWANGCHEON-DONG, SEO-GU, GWANGJU 502-801
8 CHOI BYUNG YUL NA-203 LG CHEMICAL SATAIK 1 SONGWOL-DONG, NAJU-SI, JEOLLANAM-DO 520-130
PCT International Classification Number B01J 23/16
PCT International Application Number PCT/KR2006/003138
PCT International Filing date 2006-08-10
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 102005-0073402 2005-08-10 Republic of Korea